Nature of the liquid crystalline phase transitions in the cesium pentadecafluorooctanoate (CsPFO)-water system: the nematic-to-isotropic transition.

Abstract

Deuterium NMR spectroscopy of 2H2O has been used to monitor the magnetic-field-induced order on approaching a transition to a nematic phase in isotropic solutions of disklike micelles of cesium pentadecafluorooctanoate. Highly accurate data on the phase boundaries and spinodals have been obtained for solutions with volume fraction concentration straight phi between 0.078 and 0.201. The quantity TIN-T*, where T* is the spinodal limit of the isotropic phase and TIN is the temperature at which the nematic phase first appears on cooling, decreases linearly with decreasing concentration, extrapolating to zero only at zero concentration. Thus, there is no evidence to support the presence of a Landau point along the transition line as has previously been conjectured. The values for (TIN-T*)/TIN are in the range 10(-5)-10(-4), up to two orders of magnitude smaller than corresponding values reported for calamitic thermotropic nematics. The transition gap (phiNI-phiIN)/phiIN approximately 0.33% for phi<0.20 is also very small, although finite as required for a first-order phase transition. These data, when combined with previously measured properties, present an intriguing picture of the isotropic-to-nematic phase transition in a paradigmatic system of self-assembled diskotic particles. However, it is not completely clear, within the context of current theoretical understanding, whether the behavior of this system is explicable by hard-particle models, or if the self-assembly plays a crucial role in weakening the phase transition.